Rinsing formulation for textiles

ABSTRACT

Formulation for rinsing textile fiber articles in an aqueous or aqueous-alcoholic medium, comprising an active substance comprising a liquid or solid, hydrophobic organic or organosilicon material in particulate form, a surfactant and a vehicle comprising a water-soluble organic polymer, the vehicle being capable of bringing said active substance to the surface of said textile fiber articles in the rinsing operation.

The present invention relates to an improved formulation intended forthe rinsing of textile fiber articles, comprising a hydrophobic activesubstance comprising a solid or liquid, particulate organic ororganosilicon material.

It is known to use hydrophobic organic or organosilicon materials intextile rinsing compositions.

Patent U.S. Pat. No. 4,818,242 describes an aqueous rinsing formulationwhich facilitates ironing, comprising a silicone oil cationicallydispersed in water, a fatty acid-polyamine condensate, and a cationicfilm-forming agent.

Patent U.S. Pat. No. 4,923,622 proposes rinse compositions comprising anemulsifiable concentrate which comprises cationic surfactants and an oilcapable of exhibiting lubricating properties with regard to textiles tobe treated, such as mineral oils and vegetable oils containing 8 to 22carbon atoms, and fatty acid esters.

The Applicant has found that the addition, to a formulation comprisingparticles of insoluble organic or organosilicon hydrophobic activesubstance and intended for the rinsing of textile fiber articles, of asmall amount of an appropriately selected soluble vehicle for saidactive substance makes it possible to improve significantly thedeposition of particles on the surface of said articles and hence toconfer notable benefits on said articles, such as benefits oflubrication, of softness to the touch, of antiwrinkle properties and/oreasy-iron properties and/or soil release properties, and of abrasionresistance.

The invention first provides a formulation (F) intended for use in anoperation of rinsing (R) textile fiber articles (S) by means of anaqueous or aqueous-alcoholic medium (MR), said formulation (F)

-   -   comprising at least one active substance (A) comprising at least        one solid or liquid organic or organosilicon material in        particulate form and a vehicle (V) comprising at least one        organic polymer, capable of taking said active substance (A) to        the surface of said textile fiber articles (S) in the rinsing        operation (R),    -   in the form:        -   of a stable dispersion, with a pH of from 2 to 5, of said            active substance (A) in an aqueous or aqueous-alcoholic            medium (MAV) comprising said vehicle (V), or        -   in a solid form obtained by drying said dispersion,        -    the nature of the active substance (A), of the aqueous or            aqueous-alcoholic medium (MAV), and of the vehicle (V) being            such that            -   the active substance (A)                -   is insoluble in the medium (MAV),                -   has an overall zero or cationic charge in the medium                    (MAV),                -   is stabilized in the medium (MAV) by means of a                    cationic surfactant (TAC), it being possible for                    said cationic surfactant (TAC) to be wholly or                    partly replaced by a nonionic surfactant when the                    material constituting the active substance (A) is                    intrinsically cationic or intrinsically potentially                    cationic in the medium (MAV),                -   remains insoluble in the rinsing medium (MR);            -   the vehicle (V)                -   is soluble or dispersible in the medium (MAV) and in                    the rinsing medium (MR)                -   has an overall cationic or zero ionic charge in the                    medium (MAV),                -   at the pH of the rinsing operation in the rinsing                    medium (MR) is capable of developing anionic charges                    in sufficient quantity to destabilize the active                    substance (A) in the rinsing medium (MR).

The formulation according to the invention is intended for use equallyfor implementing a washing machine rinsing operation as a hand rinsingoperation. This operation is commonly carried out at a pH which canrange from 5.5 to 8 (pH of the supply circuit water); it usually takesplace at ambient temperature. In a conventional laundry washingoperation, the rinsing formulation is employed in the final rinse.

A particle dispersion is considered as being stable if no sedimentation,phase separation or development of turbidity is observed over time. Thisdispersion is destabilized when the particles undergo aggregation withone another.

According to the invention the active substance (A) is considered asbeing destabilized in the rinsing medium (MR) comprising the vehicle (V)when the size of the objects in the dispersion is at least twice that ofthe same objects in the absence of vehicle (V).

According to the invention the active substance (A) is in a solid orliquid organic or organosilicon material in particulate form which isinsoluble in the medium (MAV), has an overall zero or cationic charge inthe medium (MAV), and remains insoluble in the rinsing medium (MR).

According to the invention the material constituting the activesubstance (A) is considered as being insoluble when less than 15%,preferably less than 10%, of its weight is soluble in the medium (MAV)and the rinsing medium (MR).

Said material constituting the active substance (A) is in particulatesoluble or liquid form. Preferentially it is in the form of an oil or ameltable solid (a wave for example).

Said particles may have an average diameter ranging from 10 nm to 200μm, preferably from 10 nm to 5 μm and more preferably from 10 nm to 2000 nm.

The diameter of said particles may be determined in well-known fashionby light scattering, by laser diffraction or by microscopy.

Among the materials which may constitute the active substance (A)mention may be made in particular of those having a lubricating actionwhich are capable of conferring on the textile fiber articles propertiesof lubrication, which may be manifested in the provision of benefitssuch as softness, wrinkle resistance, ease of ironing, abrasionresistance, soil release, etc.

According to a first embodiment of the invention said materialconstituting the active substance (A) is an organosilicon material.

It is in particular a linear, cyclic, branched or crosslinkedpolyorganosiloxane resin, wax or oil. Said polyorganosiloxane preferablyhas a dynamic viscosity, measured at 25° C. and at a shear rate of 0.01Hz for a stress of 1 500 Pa (carried out on a Carrimed® of typeCSL2-500), of between 10⁴ and 10⁹ cP. According to the invention it is:

-   -   a nonionic polyorganosiloxane    -   a polyorganosiloxane having at least one cationic or potentially        cationic function in the medium (MAV)    -   an amphoteric polyorganosiloxane having at least one cationic or        potentially cationic function in the medium (MAV) and at least        one function which is neutral in the medium (MAV) and        potentially anionic in the rinsing medium (MR)    -   a polyorganosiloxane having at least one function which is        neutral in the medium (MAV) and potentially anionic in the        rinsing medium (MR).

Examples of polyorganosiloxanes that may be mentioned include

-   -   linear, cyclic or crosslinked polyorganosiloxanes formed of        nonionic organosiloxane units of general formula        (R)_(a)(X)_(b)Si(O)_([4−(a+b)]/2)  (I)    -    in which formula    -   the symbols R are identical or different and represent a linear        or branched alkyl hydrocarbon radical having 1 to 4 carbon atoms        or an aryl radical, phenyl in particular;    -   the symbols X are identical or different and represent a        hydroxyl group, a linear or branched alkoxy radical having 1 to        12 carbon atoms, or a functional group OCOR′, where R′        represents an alkyl group containing 1 to 12 carbon atoms,        preferably 1 carbon atom;    -   a is 0, 1, 2 or 3    -   b is 0, 1, 2 or 3    -   a+b is 0, 1, 2 or 3

Preferentially said polyorganosiloxane is at least substantially linear,and very preferably is linear. By way of example mention may be made inparticular of α-ω-bis(hydroxy)polydimethylsiloxane oils,α-ω-bis(trimethyl)polydimethylsiloxane oils, cyclicpolydimethylsiloxanes, and polymethylphenylsiloxanes.

-   -   linear, cyclic or crosslinked polyorganosiloxanes comprising per        mole at least one ionic or nonionic organosiloxane unit of        general formula        (R)_(a)(X)_(b)(B)_(c)Si(O)_([4−(a+b+c)]/2)  (II)    -    in which formula    -   the symbols R are identical or different and represent a linear        or branched monovalent alkyl hydrocarbon radical having 1 to 4        carbon atoms or an aryl radical, phenyl in particular;    -   the symbols X are identical or different and represent a        hydroxyl group, a linear or branched alkoxy radical having 1 to        12 carbon atoms or a functional group OCOR′, where R′ represents        an alkyl group containing 1 to 12 carbon atoms, preferably 1        carbon atom;    -   the symbols B are identical or different and represent an        aliphatic and/or aromatic and/or cyclic hydrocarbon radical        containing up to 30 carbon atoms, optionally interrupted by one        or more oxygen and/or nitrogen and/or sulfur heteroatoms,        optionally carrying one or more ether, ester, thiol, hydroxyl,        optionally quaternized amine or carboxylate functions, the        symbol B being linked to the silicon preferably by way of an        Si—C— bond;    -   a is 0, 1 or 2    -   b is 0, 1 or 2    -   c is 1 or 2    -   a+b+c is 1, 2 or 3

The other organosiloxane units present besides those of formula (II) arepreferably nonionic and of formula (I) above.

Organosiloxane units having one or more strong anionic functions ofsulfonate and/or phosphonate type may also be present when the units offormula (II) are cationic or potentially cationic in the medium (MAV).They are present, however, in limited quantity, in order that saidpolyorganosiloxane has an overall zero or cationic charge in the medium(MAV).

By way of example of substituents corresponding to the symbol (B) in theformula (II) above, mention may be made of

-   -   polyether groups of formula        —(CH₂)_(n)—(OC₂H₄)_(m)—(OC₃H₆)_(p)—OR′    -    where n is 2 or 3, m and p are each from 0 to 30, and R′        represents an alkyl radical containing 1 to 12 carbon atoms,        preferably 1 to 4 carbon atoms.    -   primary, secondary, tertiary or quaternized amino groups, such        as those of formula        —R¹—N(R²)(R³)    -    where    -   the symbol R¹ represents an alkylene group containing 2 to 6        carbon atoms, optionally substituted or interrupted by one or        more nitrogen or oxygen atoms,    -   the symbols R² and R³, identical or different, represent        -   H,        -   an alkyl or hydroxyalkyl group containing 1 to 12 carbon            atoms, preferably 1 to 6 carbon atoms,        -   an aminoalkyl group, preferably primary, whose alkyl group            contains 1 to 12 carbon atoms, preferably 1 to 6 carbon            atoms, optionally substituted and/or interrupted by at least            one nitrogen and/or oxygen atom,    -    said amino group being optionally quaternized, for example, by        a hydrohalic acid or an alkyl or aryl halide.

Mention may be made in particular of those of formulae —(CH₂)₃NH₂—(CH₂)₃NH₃ ⁺X⁻—(CH₂)₃N(CH₃)₂ —(CH₂)₃N⁺(CH₃)₂(C₁₈H₃₇)X⁻—(CH₂)₃NHCH₂CH₂NH₂—(CH₂)₃N(CH₂CH₂OH)₂ —(CH₂)₃N(CH₂CH₂NH₂)₂

Preferentially the polyorganosiloxanes which carry amino functions havein their chain, per 100 total silicon atoms, from 0.1 to 50, preferablyfrom 0.3 to 10, and very particularly from 0.5 to 5 amino-functionalizedsilicon atoms.

-   -   sterically hindered piperidyl groups of formula III    -    where        -   R⁴ is a divalent hydrocarbon radical selected from:            -   linear or branched alkylene radicals having 2 to 18                carbon atoms;            -   alkylene-carbonyl radicals whose alkylene moiety is                linear or branched and contains 2 to 20 carbon atoms;            -   alkylene-cyclohexylene radicals whose alkylene moiety is                linear or branched and contains 2 to 12 carbon atoms and                whose cyclohexylene moiety contains an OH group and                optionally 1 or 2 alkyl radicals having 1 to 4 carbon                atoms;            -   radicals of formula —R⁷—O—R⁷ in which the radicals R⁷                are identical or different and represent alkylene                radicals having 1 to 12 carbon atoms;            -   radicals of formula —R⁷—O—R⁷ in which the radicals R⁷                have the meanings indicated above and one of them or                both are substituted by one or two —OH group(s);            -   radicals of formula —R⁷—COO—R⁷ in which the radicals R⁷                have the meanings indicated above;            -   radicals of formula —R⁸—O—R⁹—O—CO—R⁸ in which the                radicals R⁸ and R⁹ are identical or different and                represent alkylene radicals having 2 to 12 carbon atoms                and the radical R⁹ is optionally substituted by a                hydroxyl radical;            -   U represents —O— or —NR¹⁰—, R¹⁰ being a radical selected                from a hydrogen atom, a linear or branched alkyl radical                containing 1 to 6 carbon atoms, and a divalent radical                of formula:            -    in which R⁴ has the meaning indicated above, R⁵ and R⁶                have the meanings indicated below, and R¹¹ represents a                linear or branched divalent alkylene radical having 1 to                12 carbon atoms, one of the valence bonds (that of R¹¹)                being connected to the atom of —NR¹⁰—, the other (that                of R⁴) being connected to a silicon atom;        -   the radicals R⁵ are identical or different and are selected            from linear or branched alkyl radicals having 1 to 3 carbon            atoms and the phenyl radical;        -   the radical R⁶ represents a hydrogen radical or the radical            R⁵ or O..    -   or sterically hindered piperidyl groups of formula IV    -    where        -   R′⁴ is selected from a trivalent radical of formula:        -    where m represents a number from 2 to 20,        -    and a trivalent radical of formula:        -    where p represents a number from 2 to 20;        -   U′ represents —O— or NR¹²—, R¹² being a radical selected            from a hydrogen atom and a linear or branched alkyl radical            containing 1 to 6 carbon atoms;    -   R⁵ and R⁶ have the same meanings as those given above in        relation to the formula III.

Preferentially said amino-functional polyorganosiloxanes arepolyorganosiloxanes containing a sterically hindered piperidyl function,especially those which can be prepared by the process described inEP-A-659930.

Very preferably said polyorganosiloxane containing a sterically hinderedamino function is a linear, cyclic or three-dimensionalpolyorganosiloxane of formula (V):

-   -   in which:    -   (1) the symbols Z, identical or different, represent R¹ below        and/or B;    -   (2) the symbols R¹, R² and R³, identical and/or different,        represent a monovalent hydrocarbon radical selected from linear        or branched alkyl radicals having 1 to 4 carbon atoms, linear or        branched alkoxy radicals having 1 to 4 carbon atoms, a phenyl        radical and, preferably, a hydroxyl radical, an ethoxy radical,        a methoxy radical or a methyl radical;    -   (3) the symbols B, functional groups which are identical and/or        different, represent a group containing sterically hindered        piperidyl function(s), selected from those mentioned above; and    -   (4) the number of units ηSi without a group B is from 10 to 450,        preferably from 50 to 250;        -   the number of units ηSi with a group B is from 1 to 5,            preferably from 1 to 3;        -   0≦w≦10 and 8<y<448.

Very preferably said polyorganosiloxane is linear.

According to a second embodiment of the invention, said materialconstituting the active substance (A) is an organic material.

By way of example mention may be made of

-   -   mono-, di- or triglycerides of C₁-C₃₀ carboxylic acids or        mixtures thereof, such as vegetable oils (colza oil, castor oil,        sunflower oil, erucic rapeseed oil, linseed oil, etc.)    -   sugar esters, sucroglycerides    -   —C₁-C₃₀ alcohol esters of C₁-C₃₀ carboxylic or C₂-C₃₀        dicarboxylic acids    -   ethylene or propylene glycol monoesters or diesters of C₁-C₃₀        carboxylic acids    -   propylene glycol C₄-C₂₀ alkyl ethers    -   di(C₈-C₃₀ alkyl) ethers    -   organic waxes comprising alkyl chains containing 4 to 40 carbon        atoms. Among waxes mention may be made in particular of:        -   animal waxes (beeswax, lanolin, whale oil)        -   plant waxes (carnauba wax, candelilla wax, sugar cane wax,            jojoba)        -   mineral waxes (montan, ozokerite, Utah wax)        -   hydrocarbon waxes containing 4 to 35 carbon atoms (mineral            oils, paraffins, microcrystalline waxes)        -   synthetic waxes such as polyolefins (polyethylene and            polypropylene), sterone, and carbowax.

According to the invention the active substance (A) is dispersed stablyin the medium (MAV) by means of a surfactant (TAC).

Said surfactant (TAC) may be a nonionic surfactant and/or a cationicsurfactant when the material constituting the active substance (A) isintrinsically cationic or intrinsically potentially cationic in themedium (MAV).

Said surfactant (TAC) is a cationic surfactant or a mixture of cationicsurfactant and nonionic surfactant when said material constituting theactive substance (A) is uncharged or has a zero charge; the amount ofnonionic surfactant represents less than 70% of the weight of all of thesurfactants (TAC).

For effective realization of the invention the ratio of the mass ofpolymer constituting the active substance (A) to the mass of surfactant(TAC) is from 0.01 to 10, preferably from 0.01 to 1.

The cationic charges generated by the optional cationic or potentiallycationic functions of the active substance (A) and by the cationicsurfactant or surfactants at the surface of the active active substance(A) in dispersion in the medium (MAV) are such that the zeta potentialof the active substance in dispersion in (MAV) is from 0 to +50 mV,preferably from +10 to +40 mV.

Among cationic surfactants mention may be made in particular of thequaternary ammonium salts of formulaR¹R²R³R⁴N⁺X⁻where

-   -   R¹, R² and R³, alike or different, represent H or an alkyl group        containing less than 4 carbon atoms, preferably 1 or 2 carbon        atom(s), which is optionally substituted by one or more hydroxyl        function(s), or may form, together with the nitrogen atom N⁺, at        least one aromatic or heterocyclic ring,    -   R⁴ represents a C₈-C₂₂, preferably C₁₂-C₂₂, alkyl or alkenyl        group, an aryl group or benzyl, and    -   X⁻ is a solubilizing anion such as halide (for example,        chloride, bromide or iodide), sulfate or alkyl sulfate (methyl        sulfate), carboxylate (acetate, propionate or benzoate) or        alkyl- or arylsulfonate. Mention may be made in particular of        dodecyltrimethylammonium bromide, tetradecyltrimethylammonium        bromide, and cetyltrimethylammonium bromide, stearylpyridinium        chloride, Rhodaquat® TFR and Rhodamine® C15, sold by Rhodia,        cetyltrimethylammonium chloride (Dehyquart ACA and/or AOR from        Cognis), and cocobis(2-hydroxyethyl)ethylammonium chloride        (Ethoquad C12 from Akso Nobel).

Mention may also be made of other cationic surfactants having softeningproperties, such as:

-   -   the quaternary ammonium salts of formula        R^(1′)R^(2′)R^(3′)R^(4′)N⁺X⁻    -    where    -   R^(1′) and R^(2′), alike or different, represent H or an alkyl        group containing less than 4 carbon atoms, preferably 1 or 2        carbon atom(s), which is optionally substituted by one or more        hydroxyl function(s), or may form, together with the nitrogen        atom N⁺, a heterocyclic ring,    -   R^(3′) and R^(4′) represent a C₈-C₂₂, preferably C₁₀-C₂₂, alkyl        or alkenyl group, an aryl group or benzyl, and    -   X⁻ is an anion such as halide (for example, chloride, bromide or        iodide), sulfate or alkyl sulfate (methyl sulfate), carboxylate        (acetate, propionate or benzoate) or alkyl- or arylsulfonate.

The following may be mentioned in particular: dialkyldimethylammoniumchlorides such as ditallow dimethylammonium chloride or methyl sulfate,etc., and alkylbenzyldimethylammonium chlorides.

-   -   C₁₀-C₂₋₅alkylimidazolium salts such as C₁₀-C₂₅alkylimidazolinium        methyl sulfates    -   substituted polyamine salts such as        N-tallow-N,N′,N′-triethanol-1,3-propylenediamine dichloride or        dimethyl sulfate and        N-tallow-N,N,N′,N′,N′-pentamethyl-1,3-propylenediamine        dichloride

Among nonionic surfactants mention may be made of polyoxyalkenylatedderivatives such as

-   -   ethoxylated or ethoxy-propoxylated fatty alcohols    -   ethoxylated or ethoxy-propoxylated triglycerides    -   ethoxylated or ethoxy-propoxylated fatty acids    -   ethoxylated or ethoxy-propoxylated sorbitan esters    -   ethoxylated or ethoxy-propoxylated fatty amines    -   ethoxylated or ethoxy-propoxylated di(1-phenylethyl)phenols    -   ethoxylated or ethoxy-propoxylated tri(1-phenylethyl)phenols    -   ethoxylated or ethoxy-propoxylated alkyl phenols

The dispersion medium (MAV) for the active substance (A) is an aqueousor aqueous-alcoholic polar medium.

Alcohols which may be present include ethanol, isopropanol, propyleneglycol, butoxy ethanol, etc. These alcohols may represent up to 70% ofthe volume of medium (MAV)

Preferentially the medium (MAV) is water.

The medium may be brought to the desired pH of from 2 to 5 by additionof an acid, such as hydrochloric acid, citric acid, phosphoric acid,benzoic acid, etc.

The rinsing formulation (F) forming the subject of the inventioncomprises a vehicle (V) which is capable of bringing the activesubstance (A) onto the surface of the textile fiber articles in therinsing operation.

According to the invention said vehicle (V)

-   -   comprises an organic polymer which is soluble or dispersible in        the medium (MAV) and in the rinsing medium (MR)    -   has an overall cationic or zero ionic charge in the medium (MAV)    -   is capable, at the pH of the rinsing operation in the rinsing        medium (MR), of developing anionic charges in sufficient        quantity to destabilize the active substance (A) in the rinsing        medium (MR).

Said organic polymer constituting the vehicle (V) may be any polymerwhich is soluble or dispersible in aqueous or aqueous-alcoholic mediumwith a pH of between 2 and 8 and which comprises at least one unit whichis neutral in the medium (MAV) and potentially anionic (HA) in therinsing medium (MR).

They may further comprise at least one unit which is cationic orpotentially cationic (HC) in the medium (MAV) and/or at least onehydrophilic or hydrophobic nonionic unit.

The term “dispersible” signifies that the vehicle (V) does not form amacroscopic precipitate in aqueous or aqueous-alcoholic medium.

Preferentially the polymer constituting the vehicle (V) is a copolymercomprising:

-   -   at least one hydrophilic unit which is neutral in the medium        (MAV) and potentially anionic (HA) in the rinsing medium (MR)        and    -   at least one hydrophilic unit which is cationic or potentially        cationic (HC) in the medium (MAV)    -   and optionally at least one hydrophobic or hydrophilic nonionic        unit.

The polymer constituting the vehicle (V) may optionally contain anionicunits (whose first pKa is less than 3), but in a very small amount, forexample in an amount much less than 5% by weight relative to theentirety of the units.

The relative amounts of the various units of the polymer constitutingthe vehicle (V) are such that in the medium (MAV) the overall charge ofthe polymer or copolymer is zero or cationic.

The relative amounts of vehicle (V) polymer, cationic surfactant (TAC),and material constituting the active substance (A) are such that in thecourse of the rinsing operation the number of anionic charges developedin the rinsing medium (MR) by the vehicle polymer (V) is sufficient todestabilize the active substance (A) in the rinsing medium (MR), inparticular by electrostatic attraction with the surface charges of theactive substance (A) in the medium (MR).

According to the invention the active substance (A) is considered asbeing destabilized in the rinsing medium (MR) comprising the vehicle (V)when the turbidity of said medium reaches in less than 5 minutes a valueat least 5 times greater than the turbidity that the same medium wouldhave in the absence of vehicle (V).

The number of anionic charges developed in the rinsing medium (MR) bythe vehicle (V) polymer to destabilize the active substance ispreferably at least 1% relative to the number of cationic surfacecharges of the active substance (A) in the medium (MR).

This number of anionic charges may range up to 200% relative to thenumber of cationic surface charges of the active substance (A) in themedium (MR).

Possible examples that may be mentioned of polymers which may constitutethe vehicle (V) include in particular the polymers derived fromethylenically unsaturated monomers, and also natural polysaccharides andsubstituted or modified polysaccharides, and also mixtures of saidpolymers derived from ethylenically unsaturated monomers and saidpolysaccharides.

The term “polymer” is used here to denote both a homopolymer and acopolymer. The term copolymer will be used when the polymer in questionis derived from at least least two monomers of different type.

A first example of polymers which may constitute the vehicle (V) are thepolymers derived:

-   -   0 from at least one α-β monoethylenically unsaturated monomer        which is neutral in the medium (MAV) and potentially anionic        (HA) in the rinsing medium (MR) and    -   optionally at least one α-β monoethylenically unsaturated        monomer which is cationic or potentially cationic (HC) in the        medium (MAV), and    -   optionally at least one nonionic α-β monoethylenically        unsaturated monomer which is hydrophilic or hydrophobic,        preferably hydrophilic.

Preferentially the (V) is a random, block or graft copolymer derived

-   -   from at least one α-β monoethylenically unsaturated hydrophilic        monomer which is neutral in the medium (MAV) and potentially        anionic (HA) in the rinsing medium (MR) and    -   from at least one α-β monoethylenically unsaturated hydrophilic        monomer which is cationic or potentially cationic (HC) in the        medium (MAV),    -   and optionally from at least one nonionic α-β monoethylenically        unsaturated monomer which is hydrophilic or hydrophobic,        preferably hydrophilic.

The relative amounts of monomers from which (V) is derived are such thatin the medium (MAV) the overall charge of the copolymer (V) is zero orcationic.

The average molar mass of said polymer or copolymer (V) derived from oneor more α-β monoethylenically unsaturated monomers (measured by aqueousgel permeation chromatography (GPC) and expressed in polyoxyethyleneequivalents) is greater than 5 000 g/mol, generally of the order of from20 000 to 500 000 g/mol.

As examples of hydrophilic α-β monoethylenically unsaturated monomerwhich is neutral in the medium (MAV) and potentially anionic (HA) in therinsing medium (MR) mention may be made of

-   -   monomers possessing at least one carboxyl function, such as α-β        ethylenically unsaturated carboxylic acids or the corresponding        anhydrides, such as acrylic, methacrylic, and maleic acid or        anhydride, fumaric acid, itaconic acid, N-methacryloylalanine,        N-acryloylglycine and their water-soluble salts    -   monomers which are precursors of carboxylic functions, such as        tert-butyl acrylate, which give rise, after polymerization, to        carboxylic functions by hydrolysis.

As examples of hydrophilic α-β monoethylenically unsaturated monomerwhich is cationic or potentially cationic (HC) in the medium (MAV)mention may be made of

-   -   acryloyl- or acryloyloxyammonium monomers such as        trimethylammonium propyl methacrylate chloride,        trimethylammoniumethylacrylamide or -methacrylamide chloride or        bromide, trimethylammoniumbutylacrylamide or -methacrylamide        methyl sulfate, trimethylammoniumpropylmethacrylamide methyl        sulfate (MES), (3-methacrylamidopropyl)trimethylammonium        chloride (MAPTAC), (3-acrylamidopropyl)trimethylammonium        chloride (APTAC), methacryloyloxyethyltrimethylammonium chloride        or methyl sulfate, and acryloyloxyethyltrimethylammonium        chloride;    -   1-ethyl-2-vinylpyridinium or 1-ethyl-4-vinylpyridinium bromide,        chloride or methyl sulfate;    -   N,N-dialkyldiallylamine monomers such as        N,N-dimethyldiallylammonium chloride (DADMAC);    -   polyquaternary monomers such as        dimethylaminopropylmethacrylamide chloride and        N-(3-chloro-2-hydroxypropyl)trimethylammonium (DIQUAT), etc.    -   carboxybetaine monomers    -   N,N-(dialkylamino-co-alkyl)amides of α-β monoethylenically        unsaturated carboxylic acids such as        N,N-dimethylaminomethylacrylamide or -methacrylamide,        2-(N,N-dimethylamino)ethylacrylamide or -methacrylamide,        3-(N,N-dimethylamino)propyl-acrylamide or -methacrylamide, and        4-(N,N-dimethylamino)butyl-acrylamide or -methacrylamide    -   α-β monoethylenically unsaturated amino esters such as        2-(dimethylamino)ethyl methacrylate (DMAM),        3-(dimethylamino)propyl methacrylate, 2-(tert-butylamino)ethyl        methacrylate, 2-(dipentylamino)ethyl methacrylate, and        2-(diethylamino)ethyl methacrylate    -   monomers which are precursors of amine functions, such as        N-vinylformamide, N-vinylacetamide, etc., which give rise to        primary amine functions by simple acid or base hydrolysis.

As examples of hydrophilic α-β monoethylenically unsaturated monomerswhich are uncharged or unionizable mention may be made of

-   -   hydroxyalkyl esters of α-β ethylenically unsaturated acids, such        as hydroxyethyl and hydroxypropyl acrylate and methacrylate,        glyceryl monomethacrylate, etc.    -   α-β ethylenically unsaturated amides such as acrylamide,        N,N-dimethylmethacrylamide, N-methylolacrylamide, etc.    -   α-β ethylenically unsaturated monomers bearing a water-soluble        polyoxyalkylene segment of the polyethylene oxide type, such as        polyethylene oxide α-methacrylates (Bisomer S20W, SLOW, etc.,        from Laporte) or α,ω-dimethacrylates, Sipomer BEM from Rhodia        (ω-behenyl polyoxyethylene methacrylate), and Sipomer SEM-25        from Rhodia (ω-tristyrylphenyl polyoxyethylene methacrylate),        etc.    -   α-β ethylenically unsaturated monomers which are precursors of        hydrophilic units or blocks, such as vinyl acetate, which, once        polymerized, can be hydrolyzed in order to give rise to vinyl        alcohol units or polyvinyl alcohol blocks    -   α-β ethylenically unsaturated monomers of ureido type, and in        particular 2-imidazolidinone-ethyl methacrylamide (Sipomer WAM        II from Rhodia).

By way of examples of hydrophobic nonionic α-β monoethylenicallyunsaturated monomers mention may be made of

-   -   vinylaromatic monomers such as styrene, vinyltoluene, etc.    -   alkyl esters of α-β monoethylenically unsaturated acids, such as        methyl and ethyl acrylate and methacrylate, etc.    -   vinyl or allyl esters of saturated carboxylic acids, such as        vinyl or allyl acetates, propionates, and versatates    -   α-β monoethylenically unsaturated nitriles such as        acrylonitrile, etc.

As examples of hydrophilic anionic α-β monoethylenically unsaturatedmonomer (whose first pKa is less than 3) mention may be made of

-   -   monomers possessing at least one sulfate or sulfonate function,        such as 2-sulfooxyethyl methacrylate, vinylbenzene sulfonic        acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic        acid, sulfoethyl acrylate or methacrylate, sulfopropyl acrylate        or methacrylate and their water-soluble salts    -   monomers possessing at least one phosphonate or phosphate        function, such as vinylphosphonic acid, etc., the esters of        ethylenically unsaturated phosphates, such as the phosphates        derived from hydroxyethyl methacrylate (Empicryl 6835 from        Rhodia) and those derived from polyoxyalkylene methacrylates,        and their water-soluble salts.

By way of examples of polymers derived from ethylenically unsaturatedmonomers constituting the vehicle (V) mention may be made of:

-   -   polyacrylic or polymethacrylic acids, alkali metal polyacrylates        or polymethacrylates, preferably with a molar mass by weight of        from 100 000 to 1 000 000 g/mol    -   acrylic acid/DADMAC copolymers, with a molar ratio of 50/50 to        30/70, preferably with a molar mass by weight of from 70 000 to        350 000 g/mol    -   acrylic acid/MAPTAC copolymers, with a molar ratio of 60/40 to        30/70, preferably with a molar mass by weight of from 90 000 to        300 000 g/mol    -   acrylic acid/MAPTAC/linear C₄-C₁₈ alkyl methacrylate terpolymers        comprising 0.005 to 10% by mass of alkyl methacrylate, with an        acrylic acid/MAPTAC molar ratio ranging from 60/40 to 30/70, and        preferably having a molar mass by weight of from 50 000 to 250        000 g/mol    -   acrylic acid/dimethylaminoethyl methacrylate (DMAEMA)        copolymers, with a molar ratio of 60/40 to 30/70, preferably        with a molar mass by weight of from 50 000 to 300 000 g/mol.

A second example of polymers which can constitute the vehicle (V) arepotentially anionic natural polysaccharides and potentially anionic oramphoteric substituted or modified polysaccharides.

The potentially anionic natural polysaccharides are formed of nonionicmonosaccharide units and of monosaccharide units which are neutral inthe medium (MAV) and potentially anionic in the rinsing medium (MR),these units being alike or different. They may be linear or branched.

More particularly said potentially anionic natural polysaccharides arebranched polysaccharides formed

-   -   of a main chain comprising alike or different anhydrohexose        units    -   and of branches comprising at least one anhydropentose and/or        anhydrohexose unit which is neutral in the medium (MAV) and        optionally potentially anionic in the rinsing medium (MR).

The hexose units (alike or different) of the main chain may be units ofD-glucose, D- or L-galactose, D-mannose, D- or L-fucose, L-rhamnose,etc.

The pentose and/or hexose units (alike or different) which are nonionicor neutral in the medium (MAV) and potentially anionic in the medium(MR) of the branches may be units of D-xylose etc., L- or D-arabinose,D-glucose, D- or L-galactose, D-mannose, D- or L-fucose, L-rhamnose,D-glucuronic acid, D-galacturonic acid, D-mannuronic acid, D-mannosesubstituted by a pyruvic group, etc.

By way of examples of natural polysaccharides which are neutral in themedium (MAV) and potentially anionic in the rinsing medium (MR) mentionmay be made of xanthan gum (such as the Rhodopol® products from Rhodia),succinoglycans, rhamsans, gellan gums, welan gums, etc.

Their molar mass by weight may range from 2 000 to 5 000 000, preferablyfrom 10 000 to 5 000 000, more particularly from 10 000 to 4 000 000g/mol.

The molar mass by weight Mw of said polysaccharides may be measured bysize exclusion chromatography.

When the polysaccharides in question are substituted or modified, theirnative skeleton is formed of nonionic monosaccharide units and/or ofmonosaccharide units which are neutral in the medium (MAV) andpotentially anionic in the rinsing medium (MR), said monosaccharideunits being alike or different and being substituted or modified:

-   -   by one or more groups which carry at least one charge which is        neutral in the medium (MAV) and potentially anionic in the        medium (MR)    -   and optionally by one or more groups which carry at least one        charge which is cationic or potentially cationic in the medium        (MAV),    -    the degree of substitution or modification of the        monosaccharide units by the entirety of the groups which carry        charges which are potentially anionic and of optional groups        which carry cationic charges being such that said substituted or        modified polysaccharide is soluble or dispersible in aqueous or        aqueous-alcoholic medium and has an overall cationic or zero        charge in the medium (MAV).

Said substituted or modified polysaccharides may further comprise atleast one nonionic modifying or substituent group.

Among the native skeletons which can be employed mention may be made oflinear or branched polysaccharides.

More particularly said polysaccharide is a substituted or modifiedbranched polysaccharide whose native skeleton is formed

-   -   of a main chain comprising alike or different anhydrohexose        units    -   and of branches comprising at least one anhydropentose and/or        anhydrohexose unit which is neutral in the medium (MAV) and        optionally potentially anionic in the rinsing medium (MR),    -    the anhydrohexose and/or anhydropentose units of said        polysaccharide being substituted or modified by one or more        groups which carry at least one charge which is neutral in the        medium (MAV) and potentially anionic in the medium (MR) and        optionally at least one charge which is cationic or potentially        cationic in the medium (MAV),    -    the degree of substitution or modification DSi of the        anhydrohexose and/or anhydropentose units by the entirety of        said groups which carry charges which are ionic or potentially        ionic ranging from 0.01 to less than 3, preferably from 0.01 to        2.5,    -    with a ratio of the number of potentially anionic charges in        the medium (MR) to the number of cationic or potentially        cationic charges in the medium (MAV) ranging from 100/0 to        30/70, preferably from 100/0 to 50/50.

When the polysaccharide in question is amphoteric the ratio of thenumber of charges which are potentially anionic in the medium (MR) tothe number of charges which are cationic or potentially cationic in themedium (MAV) is from 99.5/0.5 to 30/70, preferably from 99.5/0.5 to50/50.

Said substituted or modified branched polysaccharide may furthercomprise at least one nonionic modifying or substituent group.

The molar mass by weight of said substituted or modified polysaccharidesmay range from 2 000 to 5 000 000, preferably from 10 000 to 5 000 000g/mol. The molar mass by weight, Mw, of said polysaccharides may bemeasured by size exclusion chromatography.

When the polysaccharide in question carries substituent groups which arepotentially anionic in the medium (MR) the measurement is made in waterat a pH of 9-10 containing 0.1 M LiCl and 2/10 000 of sodium nitrate.

When the polysaccharide in question is amphoteric, i.e., carriessubstituent groups which are potentially anionic in the medium (MR) andgroups which are cationic or potentially cationic in the medium (MAV),the measurement is made in a 0.1 M aqueous formic acid solutioncontaining 0.05 M sodium nitrate and 10 ppm of high molar masspolyallyldimethylamine chloride (PDADMA) in the case of polysaccharideswhose DSi in terms of ionic or potentially ionic function is less than0.5. For those whose DSi is greater than 0.5 a 0.025 M aqueoushydrochloric acid solution is used. The molar mass by weight, Mw, isestablished directly in a known manner by means of the light scatteringvalues.

The degree of substitution or of modification, DSi, corresponds to theaverage number of hydroxyl functions of the anhydrohexose and/oranhydropentose units which are substituted or modified by said ionic orpotentially ionic group or groups per anhydrohexose and/oranhydropentose unit.

Said ionic or potentially ionic groups are linked to the carbon atoms ofthe sugar skeleton either directly or by way of —O— bonds.

In the case of amphoteric polysaccharides the potentially anioniccharges may be provided by modifying groups or substituent groups whichare different from those which carry cationic or potentially cationiccharges; in that case said polymer is an ampholyte polysaccharide.

When a modifying group or substituent group at the same time carries apotentially anionic charge and a cationic or potentially cationiccharge, said polysaccharide is in that case of betaine type.

Said substituted or modified polysaccharide may further exhibit at leastone nonionic modifying group or substituent group. Said nonionic groupsare attached to the carbon atoms of the sugar skeleton either directlyor by way of —O— bonds. The presence of such groups is expressed innumber of moles of substitution MS, i.e., in average number of moles ofprecursor of said nonionic substituent which have reacted peranhydrohexose and/or anhydropentose unit. If said precursor is notappropriate for forming new, reactive hydroxyl groups (alkylationprecursor, for example), the degree of substitution or of modificationby the entirety of the ionic or ionizable groups and nonionic groups isless than 3 by definition. If said precursor is capable of forming new,reactive hydroxyl groups (hydroxyl alkylation precursor, for example),there is theoretically no limit on the number of moles of substitution,MS; it may, for example, be up to 6, preferably up to 2.

Among the groups which are potentially anionic in the medium (MR)mention may be made of those containing one or more carboxylate(carboxylic) functions.

Mention may be made in particular of those of formula—[—CH₂—CH(R)—O]_(x)—(CH₂)_(y)—COOH or—[—CH₂—CH(R)—O]_(x)—(CH₂)_(y)—COOMwhere

-   R is a hydrogen atom or an alkyl radical containing 1 to 4 carbon    atoms-   x is an integer ranging from 0 to 5-   y is an integer ranging from 0 to 5-   M represents an alkaline metal.

Very particular mention may be made of the carboxy groups —COO⁻Na⁺attached directly to a carbon atom of the sugar skeleton and of carboxymethyl (sodium salt) groups —CH₂—COO⁻Na⁺ attached to a carbon atom ofthe sugar skeleton via an —O— bond.

Among cationic or potentially cationic groups mention may be made ofthose which contain one or more amino, ammonium, phosphonium,pyridinium, etc., functions.

Mention may be made in particular of the cationic or potentiallycationic groups of formula

-   -   —NH₂    -   —[—CH₂—CH(R)—O]_(x)—(CH₂)_(y)—COA-R′—N(R″)₂    -   —[—CH₂—CH(R)—O]_(x)—(CH₂)_(y)—COA-R′—N⁺(R′″)₃X⁻    -   —[—CH₂—CH(R)—O]_(x)—(CH₂)_(y)—COA-R′—NH—R″″—N(R″)₂    -   —[—CH₂—CH(R)—O]_(x)—R′—N(R″)₂    -   —[—CH₂—CH(R)—O]_(x)—R′—N⁺(R′″)₃X⁻    -   —[—CH₂—CH(R)—O]_(x)—R′—NH—R″″—N(R″)₂    -   —[—CH₂—CH(R)—O]_(x)—Y—R″    -    where    -   R is a hydrogen atom or an alkyl radical containing 1 to 4        carbon atoms    -   x is an integer ranging from 0 to 5    -   y is a integer ranging from 0 to 5    -   R′ is an alkylene radical containing 1 to 12 carbon atoms,        optionally carrying one or more OH substituents    -   the radicals R″, which are alike or different, represent a        hydrogen atom or an alkyl radical containing from 1 to 18 carbon        atoms    -   the radicals R′″, which are alike or different, represent an        alkyl radical containing 1 to 18 carbon atoms    -   R″″ is a linear, branched or cyclic alkylene radical containing        1 to 6 carbon atoms    -   A represents O or NH    -   Y is a heterocyclic aliphatic group containing 5 to 20 carbon        atoms and one nitrogen heteroatom    -   X⁻ is a counterion, preferably halide (chloride, bromide and        iodide in particular),    -    and N-alkylpyridinium-yl groups whose alkyl radical contains 1        to 18 carbon atoms, with a counterion, preferably halide        (chloride, bromide and iodide in particular).

Among cationic or potentially cationic groups mention may be made veryparticularly of:

-   -   those of formula    -   —NH₂    -   —CH₂—CONH—(CH₂)₂—N(CH₃)₂    -   —CH₂—COO—(CH₂)₂—NH— (CH₂)₂—N(CH₃)₂    -   —CH₂—CONH—(CH₂)₃—NH—(CH₂)₂—N(CH₃)₂    -   —CH₂—CONH—(CH₂)₂—NH—(CH₂)₂—N(CH₃)₂    -   —CH₂—CONH—(CH₂)₂—N⁺(CH₃)₃ Cl⁻    -   —CH₂—CONH—(CH₂)₃—N⁺(CH₃)₃ Cl⁻    -   —(CH₂)₂—N(CH₃)₂    -   —(CH₂)₂—NH—(CH₂)₂—N(CH₃)₂    -   —(CH₂)₂—N⁺(CH₃)₃ Cl⁻    -   2-hydroxypropyltrimethyl ammonium chloride        —CH₂—CH(OH)—CH₂—N⁺(CH₃)₃ Cl⁻    -   pyridinium-yl groups such as N-methylpyridinium-yl groups, of        formula    -    with a chloride counterion    -   hindered amino groups such as those derived from HALS amines of        general formula    -    where R represents CH3 or H.

Among betaine groups mention may be made more particularly of thefunction of formula: —(CH₂)₂—N⁺(CH₃)₂— (CH₂)₂—COO⁻, anethyldimethylammonium betaine function.

Among nonionic groups mention may be made of those of formula:—[—CH₂—CH(R)—O]_(x)—R¹ where

-   R is a hydrogen atom or an alkyl radical containing 1 to 4 carbon    atoms-   x is an integer ranging from 0 to 5-   R¹ represents    -   a hydrogen atom    -   an alkyl radical containing 1 to 22 carbon atoms which is        optionally interrupted by one or more oxygen and/or nitrogen        heteroatoms, cycloalkyl, aryl or arylalkyl, containing 6 to 12        carbon atoms    -   a radical —(CH₂)_(y)—COOR²    -   a radical —(CH₂)_(y)—CN    -   a radical —(CH₂)_(y)—CONHR²-   where R represents an alkyl, aryl or arylalkyl radical containing 1    to 22 carbon atoms,-   and y is an integer ranging from 0 to 5    —CO—NH—R¹,-   where R¹ is as defined above,-   attached to a carbon atom of the sugar skeleton via an —O— bond.

Very particular mention may be made of the following groups:

-   -   methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dodecyl,        octadecyl, phenyl and benzyl, which are attached to a carbon        atom of the sugar skeleton by way of ether, ester, amide or        urethane linkage,    -   cyanoethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl, which        are attached to a carbon atom of the sugar skeleton by way of an        —O— bond.

The hexose units (alike or different) of the main chain of the nativeskeleton may be units of D-glucose, D- or L-galactose, D-mannose, D- orL-fucose, L-rhamnose, etc.

The pentose and/or hexose units (alike or different) which are nonionicor neutral in the medium (MAV) and potentially anionic in the medium(MR) of the branches of the native skeleton may be units of D-xylose,etc., L- or D-arabinose, D-glucose, D- or L-galactose, D-mannose, D- orL-fucose, L-rhamnose, D-glucuronic acid, D-galacturonic acid, andD-mannuronic acid.

Examples of native skeleton that may be mentioned includegalactomannanes, galactoglucomannanes, xyloglucans, xanthan gums,scleroglucans, succinoglycans, rhamsans, welan gums, etc.

Preferentially the native skeleton is a galactomannan.

The galactomannanes are macromolecules containing a main chain ofD-mannopyranose units attached in β(1-4) position which is substitutedby D-galactopyranose units in α(1-6) position. Among these mention maybe made of guar gum, carob gum, and tara gum.

Very preferentially the native skeleton is a guar gum. Guar gums have amannose/galactose ratio of 2.

The substituted or modified polysaccharides used according to theinvention may be obtained by functionalizing the native skeleton bymeans of precursors of the ionic or potentially ionic groups andoptionally nonionic groups.

These operations of functionalization may be carried out in a known wayby oxidation, substitution, condensation, and/or addition.

Examples of substituted or modified polysaccharides which can be usedaccording to the invention include

-   -   carboxymethylgalactomannans, especially carboxymethylguars,    -   carboxymethylhydroxypropylgalactomannans, especially        carboxymethylhydroxypropylguars,    -   carboxymethyl-hydroxypropyltrimethylammonium chloride        galactomannans, especially        carboxymethylhydroxypropyltrimethylammonium chloride guars,    -   carboxymethylhydroxypropyl-hydroxypropyltrimethylammonium        chloride galactomannans, especially        carboxymethyl-hydroxypropyl-hydroxypropyltrimethylammonium        chloride guars.

When the vehicle (V) is a polysaccharide it is preferable for thedispersion of the active substance (A) in the medium (MAV) comprisingthe vehicle (V) to have a pH ranging from 3.5 and in particular from 4.5to 5 when said polysaccharide is a substituted or modified guar.

For effective realization of the invention the amount of vehicle (V)present in the formulation according to the invention is from 0.001 to 5parts by weight, preferably from 0.01 to 4 parts, and more particularlyfrom 0.05 to 2 parts by weight per 100 parts by weight of activesubstance (A).

The formulation (F) according to the invention may be in the form

-   -   of a stable dispersion (liquid, cream, paste, gel, etc)    -   or in solid form (powder, granules, block, tablet, etc).

The formula (F) in the form of a stable dispersion may be obtained by

-   -   1) preparing an aqueous dispersion (emulsion, microemulsion,        suspension) of the material constituting the active        substance (A) with the aid of a surfactant (TAC) as stabilizer;    -   2) optionally diluting with water or a water/alcohol mixture        (depending on the desired proportion of active substance A in        the formulation F) and adjusting the pH to a value of 2.5-5        using an acid (hydrochloric acid, citric acid, phosphoric acid,        benzoic acid, etc);    -   3) adding the vehicle (V) to the resulting dispersion;    -   4) optionally adding an additional amount of surfactant (TAC)        before or after adding said vehicle, and    -   5) if necessary readjusting the pH to a value of from 2.5-5        using an acid.

For effective realization of the invention the aqueous oraqueous-alcoholic formulation (F) comprises per 100 parts of its weight:

-   -   from 0.01 to 40, preferably from 0.05 to 30 parts by dry weight        of active substance (A)    -   from 0.01 to 50, preferably from 0.01 to 35 parts by dry weight        of cationic surfactant (TAC)    -   from 0.001 to 4, preferably from 0.01 to 1 part by dry weight of        vehicle (V) polymer.

Said dispersion may have a solids content of from 0.021 to 90%,preferably from 0.07 to 51% by weight.

The formulation (F) in the form of a solid may be obtained by

-   -   1) preparing an aqueous dispersion of polymer constituting the        active substance (A) with the aid of a surfactant (TAC) as        stabilizer;    -   2) adjusting the pH to a value of 2.5-5 using an acid        (hydrochloric acid, citric acid, phosphoric acid, benzoic acid,        etc);    -   3) adding the vehicle (V) to the resulting dispersion;    -   4) optionally adding an additional amount of surfactant (TAC)        before or after adding said vehicle, and    -   5) if necessary readjusting the pH to a value of from 2.5-5        using an acid;    -   evaporating/drying.

The evaporating/drying step may be carried out in accordance with anymeans known to the skilled worker, in particular by lyophilization(i.e., freezing, then sublimation) or, preferably, by spray drying.

Spray drying may be carried out in any known apparatus, such as aspraying tower in combination with a spraying operation carried out by anozzle or a turbine with a stream of hot air. The implementationconditions are dependant on the type of atomizer used; these conditionsare generally such that the temperature of the entirety of the productin the course of drying is at least 30° C. and does not exceed 150° C.

The evaporating/drying step may be facilitated by the presence withinthe dispersion which is subjected to said step of a protectant, inparticular by the presence of at least one sugar, saccharide orpolysaccharide which is water-soluble or water-dispersible, preferably asugar. The amount of protectant may represent of the order of from 10 to50 parts by weight per 100 parts by weight of active substance (A).

Among sugars mention may be made of aldoses such as glucose, mannose,galactose, and ribose and of ketoses such as fructose.

The granules obtained may be ground to give a powder or compactedconventionally to give tablets, for example.

The formulation (F) may further comprise other, customary constituentsof cationic rinsing formulations.

It may in particular comprise at least one cationic and/or nonionicsoftener, such as acyclic quaternary ammonium compounds, alkoxylatedpolyamines, quaternary diamido ammonium salts, quaternary ammoniumesters, quaternary imidazolium salts, primary, secondary or tertiaryamines, alkoxylated amines, cyclic amines, nonionic sugar derivatives,etc., which are mentioned in particular in WO 00/68352. Examples of someof these cationic softeners have already been mentioned earlier on assurfactant (TAC).

The softeners may be present in a proportion of from 0.5 to 90%,preferably from 0.5 to 40%, depending on the concentration of saidformulation (F).

Also present may be:

-   -   optical brighteners (0.1 to 0.2%)    -   color transfer inhibitors (polyvinylpyrrolidone,        polyvinyloxazolidone, polymethacrylamide, etc. 0.03 to 25%,        preferably 0.1 to 15%)    -   water-soluble monovalent mineral salts, such as sodium,        potassium or ammonium chlorides, nitrates or sulfates        (especially when the vehicle (V) is a polysaccharide), in a        proportion, for example, of from 0.01 to 2 mol per liter    -   dyes,    -   fragrances,    -   foam suppressants    -   enzymes    -   bleaches.

The formulation (F) of the invention may be employed to carry out arinsing operation which follows an operation of washing—by hand or in awashing machine—textile fiber articles. Said articles may consist ofnatural and/or artificial and/or synthetic fibers.

Said formulation is especially advantageous for rinsing cotton orcotton-based articles.

It may be employed in the rinsing bath in a proportion of from 0.001 to5 g/l, preferably from 0.005 to 2 g/l, the proportion of formulationbeing expressed in terms of dry matter. This rinsing operation may becarried out at ambient temperature.

This rinsing operation makes it possible to impart to said articles, inaddition to the conventional benefits of softness which are provided bythe nonionic and/or cationic softener or softeners, properties ofwrinkle resistance (antiwrinkle properties) and/or of ease of ironing,of abrasion resistance, and soil release properties, which are providedby the deposition of the active substance (A) on the surface of saidarticles, this deposition being promoted by the presence of the vehicle(V). Advantageous soil release properties are provided in particularthrough the use as active substance (A) in the formulation (F) of asilicone oil, in particular of a silicone oil containing a hinderedpiperidyl function.

The invention secondly provides a process for treating textile fiberarticles by contacting said articles in the course of a rinsingoperation in aqueous or aqueous-alcoholic medium with the rinsingformulation (F) as described above, then recovering said rinsedarticles.

The operating conditions of such a treatment have already been mentionedabove.

The invention thirdly provides a process for enhancing the antiwrinkleand/or easy-iron and/or soil release and/or abrasion resistanceproperties of textile fiber articles which consists in contacting saidarticles in the course of a rinsing operation in aqueous oraqueous-alcoholic medium with the rinsing formulation (F) as describedabove, then in recovering said rinsed articles.

The operating conditions for carrying out such a process have alreadybeen mentioned above.

The invention fourthly provides for the use in a formulation (F)intended for use in an operation of rinsing (R) textile fiber articles(S) by means of an aqueous or aqueous-alcoholic medium (MR), formulation(F) comprising at least one active substance (A) comprising at least oneliquid or solid organic or organosilicon material in particulate formand being

-   -   in the form of a stable dispersion with a pH of from 2 to 5 of        said active substance (A) in an aqueous or aqueous-alcoholic        medium (MAV) or    -   in a solid form obtained by drying said dispersion,    -    the nature of the active substance (A) and of the aqueous or        aqueous-alcoholic medium (MAV) being such that the active        substance (A)        -   is insoluble in the medium (MAV)        -   has an overall zero or cationic charge in the medium (MAV),        -    is stabilized in the medium (MAV) by means of a cationic            surfactant (TAC), it being possible for said cationic            surfactant (TAC) to be wholly or partly replaced by a            nonionic surfactant when the material constituting the            active substance (A) is intrinsically cationic or            intrinsically potentially cationic in the medium (MAV)        -   remains insoluble in the rinsing medium (MR);    -    of at least one organic polymer which    -   is soluble or dispersible in the medium (MAV) and in the rinsing        medium (MR)    -   has an overall cationic or zero ionic charge in the medium (MAV)    -   and is capable, at the pH of the rinsing operation in the        rinsing medium (MR), of developing anionic charges in sufficient        quantity to destabilize the active substance (A) in the rinsing        medium (MR);    -    as a vehicle (V) capable of bringing said active substance (A)        toward the surface of said textile fiber articles (S) in the        rinsing operation (R).

The nature and the relative amounts of the various constituents, theirconditions of use, and the operating conditions to be employed havealready been set out above.

The object fifthly provides a process for enhancing the deposition of anactive substance (A) comprising at least one solid or liquid organic ororganosilicon material in particulate form on the surface of textilefiber articles (S), during an operation of rinsing of said articles bymeans of an aqueous or aqueous-alcoholic medium (MR) obtained from aformulation (F) comprising said active substance (A), the formulation(F) being

-   -   in the form of a stable dispersion with a pH of from 2 to 5 of        said active substance (A) in an aqueous or aqueous-alcoholic        medium (MAV) or    -   in a solid form obtained by drying said dispersion,    -    the nature of the active substance (A) and of the aqueous or        aqueous-alcoholic medium (MAV) being such that the active        substance (A)        -   is insoluble in the medium (MAV)        -   has an overall zero or cationic charge in the medium (MAV),    -   is stabilized in the medium (MAV) by means of a cationic        surfactant (TAC), it being possible for said cationic surfactant        (TAC) to be wholly or partly replaced by a nonionic surfactant        when the material constituting the active substance (A) is        intrinsically cationic or intrinsically potentially cationic in        the medium (MAV)        -   remains insoluble in the rinsing medium (MR);    -    by adding to said formulation (F) a vehicle (V) comprising at        least one organic polymer which    -   is soluble or dispersible in the medium (MAV) and in the rinsing        medium (MR)    -   has an overall cationic or zero ionic charge in the medium (MAV)    -   and is capable, at the pH of the rinsing operation in the        rinsing medium (MR), of developing anionic charges in sufficient        quantity to destabilize the active substance (A) in the rinsing        medium (MR).

The nature and the relative amounts of the various constituents, theirconditions of use and the operating conditions to be employed havealready been set out above.

The examples which follow are given by way of illustration.

EXAMPLE 1 Antiwrinkle and Easy-Iron Effect

30% of a sunflower oil of type Lubrirob® TOD18.80 (from Rhodia/Novance)is emulsified in water in a microfluidizer (4 bar, 3 cycles) withheating (50° C.) in the presence of 3% by weight of cationic surfactants(cetyltrimethylammonium bromide type).

This gives an emulsion (E) having a dry extract of 30% by weight ofactive substance, whose size, measured by laser diffraction (Horibagranulometer), is 250 nm. This size is a mass-average size of the sizedistribution of the emulsion.

This emulsion (E) is used to produce various formulations.

Formulation I1

The pH of the emulsion (E) is adjusted to 4.0 with 1 N hydrochloric acidsolution. The resulting dispersion is milky.

Under mechanical stirring 20 ml of the dispersion are poured into 1 mlof water whose pH has been adjusted to 4. This gives a mixture, pH=4,whose appearance is not significantly different from that of theoriginal dispersion. This mixture is stable for a number of days, doesnot form any precipitate and does not change in turbidity over time.

Formulation II1

The pH of the emulsion (E) is adjusted to 4.0 with 1 N hydrochloric acidsolution. The resulting dispersion is milky.

Also prepared is a 2.2% by weight aqueous solution of a 1:1 molaracrylic acid-DADMAC copolymer (with a molar mass of 100 000 g/mol)(vehicle V), the solution having been adjusted to a pH of 4.0 with 10%by weight hydrochloric acid solution.

20 ml of the dispersion of active substance (A) are poured into 1 ml ofthe vehicle (V) copolymer solution under mechanical stirring. This givesa mixture with a pH of 4 whose appearance is not significantly differentfrom that of the original dispersion. This mixture is stable for anumber of days, does not form any precipitate and does not change inturbidity over time.

Dilute Formulations I1(a) and II1(a) Obtained by Diluting FormulationsI1 and II1 in Water at a pH of 4

A Horiba granulometer vessel is introduced with water whose pH has beenadjusted to 4 (approximately 100 ml). 0.1 ml of the formulation II isadded to the vessel under mechanical stirring and the change in size ofthe emulsion over time is monitored.

The same operation is repeated with 0.1 ml of formulation II1.

The results are given in table 1. TABLE 1 Size of the Size of theemulsion in nm emulsion in nm Time (min) Formulation I1(a) FormulationII1(a) 1 525 525 5 525 525 10 525 525This size does not change over time.Dilute Formulations I1(b) and II11(b) Obtained by Diluting FormulationsI1 and II1 in Water at a pH of 7.2

The granulometer vessel is charged with water at its natural pH of 7.2(approximately 100 ml).

0.1 ml of the formulation I1 is added therein under mechanical stirringand the change in size of the emulsion over time is monitored.

The same operation is repeated with 0.1 ml of formulation II1.

The results are given in table 2. TABLE 2 Size of the Size of theemulsion in nm emulsion in nm Time (min) Formulation I1(b) FormulationII1(b) 1 525 750 5 525 1230 10 525 1800Effect of the (V)/(A) Weight Ratio: Amount of Vehicle (V)/Amount ofActive Substance (A)

The pH of the emulsion (E), containing 30% by weight of activesubstance, is adjusted to 4.0 with 1 N hydrochloric acid solution. Thedispersion obtained is milky.

Also prepared is an 11% by weight aqueous solution of a 1:1 molaracrylic acid-DADMAC copolymer (with a molar mass of 100 000 g/mol)(vehicle V), the pH of the solution having been adjusted to 4.0 with 10%by weight hydrochloric acid solution.

20 ml of the dispersion of active substance (A) are poured respectivelyinto 4 ml (formulation 1), 0.1 ml (formulation 2) and 0.05 ml(formulation 3) of the solution of vehicle (V) copolymer undermechanical stirring.

Formulations 2 and 3 are made up respectively with 3.9 ml of 3.95 ml ofwater, so as to keep the active substance (A) concentration constant.

This gives three formulations with a pH of 4 whose appearance is notsignificantly different from that of the original dispersion and inwhich the (V)/(A) weight ratios are 7.2/100, 0.18/100 and 0.09/100respectively. Three beakers are prepared each containing 200 ml of waterat its natural pH of 7.2.

0.1 ml of formulation is added to each beaker under mechanical stirring,and the change in appearance of the dispersions is monitored. (V)/(A)(V)/(A) (V)/(A) 7.2/100 0.18/100 0.09/100 Appearance Stable, milkyFlocculation Flocculation

These results show that the ratio (V)/(A) has an effect on the capacityof the vehicle (V) to cause flocculation of the active substance (V).

Washing Machine Test

The following three rinsing formulations are prepared or employed:

-   -   50 ml of a commercial softener formulation FR, containing only        cationic surfactants (15% solids)    -   a softener formulation FRI1 obtained by adding 10 ml of the        formulation I1 above, of pH=4, to 50 ml of the formulation FR,        corresponding to 196 mg of active substance (A) per liter of        water in the machine    -   a softener formulation FRII1 obtained by adding 10 ml of the        formulation II1 above, of pH=4, to 50 ml of the formulation FR,        corresponding to 190 mg of active substance (A) per liter of        water in the machine.

1.5 kg of flat cotton fabric samples measuring 50 cm×50 cm (their finishhaving been removed beforehand by three successive washes withdemineralized water at 90° C.) are washed at 30° C. using a commercialpowder detergent formulation in a Miele® washing machine (from Miele).

At the end of the wash cycle one of the samples is placed in reserve andrinsed with 15 liters of mains water at 23° C., then wrung; the rinsecycle lasts 5 minutes. The other samples are divided into three batches.

The first batch is rinsed for 5 minutes with 15 liters of mains water at23° C., to which 50 ml of formulation FR have been added, then is wrungunder the same conditions as the reserved sample.

The second batch is rinsed for 5 minutes with 15 liters of mains waterat 23° C., to which 60 ml of formulation FRI1 have been added, then iswrung under the same conditions as the reserved sample.

The third batch is rinsed for 5 minutes with 15 liters of mains water at23° C., to which 60 ml of formulation FRII1 have been added, then iswrung under the same conditions as the reserved sample.

During the rinse cycle the pH of the medium reaches 7.

After wringing, the articles are placed on a rack to dry.

After drying, a digital color photograph is taken of an area of the drysamples, which is subsequently converted into 256 levels of grey (greyscale from 0 to 255).

The number of pixels corresponding to each level of grey is counted.

For each resulting histogram the standard deviation a of thedistribution of the level of grey is measured. If wrinkling issubstantial, the distribution of the level of grey is large.

σ1 corresponds to the standard deviation corresponding to the reservedsample (rinsed without a rinsing formulation).

σ2 corresponds to the standard deviation obtained with the rinsingformulation in question.

σ3 corresponds to the standard deviation obtained on flat startingsamples which have not undergone an operation of washing, rinsing orwringing.

The performance value WR (wrinkle recovery) is given by the followingequationWR(%)=[(σ1−σ2)/σ1]f×100where f is a standardization factor, equal to 1/[(σ1−σ3)/σ1]A value of:

-   -   0% corresponds to zero benefit    -   100% corresponds to a flat surface

The results of the wrinkle test are as follows: Rinsing formulation FRFRI1(a) FRII1(a) WR 30% 38% 52%

The above results show that the addition of the vehicle (V) enhances thedeposition of the active substance (A) on the fabric, which manifestedin an improvement in the antiwrinkle effect of the active substance (A).

EXAMPLE 2 Soil Release Effect

Formulation I2

An emulsion is used which comprises 30% by weight of silicone containinghindered piperidyl functions (Rhodorsil® 21645 from Rhodia) and 3% of anonionic surfactant of ethoxylated fatty alcohol type (Symperonic A7).

Under mechanical stirring, 20 ml of the dispersion are poured into 1 mlof water whose pH has been adjusted to 4.5.

0.1 g of sodium chloride is added (for better comparison with formulaII2 below).

Formulation II2

An emulsion is used which comprises 30% by weight of silicone containinghindered piperidyl functions (Rhodorsil® 21645 from Rhodia) and 3% of anonionic surfactant of ethoxylated fatty alcohol type (Symperonic A7).

Also prepared is a 1% by weight solution of xanthan gum (Rhodopol® fromRhodia) with a molar mass by weight of 4 000 000 g/mol in water with apH of 4.5.

Under mechanical stirring, 20 ml of the dispersion are poured into 1 mlof the xanthan gum solution. The final dispersion has a pH of 4.5.

0.1 g of sodium chloride is added to stabilize the dispersion over time.

Test

The test is carried out in a Tergotometer laboratory apparatus which iswell known to the formulators of detergent compositions. The apparatussimulates the mechanical and thermal effects of the American-typewashing machines with a pulsing action; by virtue of the presence of 3washing pots, it allows series of simultaneous tests to be carried outwith a considerable time saving.

The composition of the laundry detergent employed is as follows: Partsby Composition of the laundry detergent weight Zeolite 4A 25 Lightcarbonate 15 Disilicate R2A 5 Acrylic/maleic copolymer Sokalan CP5(BASF) 5 Na sulfate 9.5 Carboxymethylcellulose 1 Perborate monohydrate15 Tetraacetylethylenediamine 5 Linear dodecylbenzenesulfonate 6Synperonic A3 (C12-C15 fatty alcohol 3 ethoxylated with 3 EO) SynperonicA9 (C12-C15 fatty alcohol 9 ethoxylated with 9 EO) Enzyme esperase 4.0 T0.5 Fragrances 1

The following three rinsing formulations are tested:

-   -   7 ml of a commercial softener formulation FR containing only        cationic surfactants (15% solids)    -   a softener formulation FRI2 obtained by adding 0.3 ml of the        formulation I2 above to 7 ml of the formulation FR,    -   a softener formulation FRII2 obtained by adding 0.3 ml of the        formulation II2 above to 7 ml of the formulation FR.        (a) Prewash/Rinsing/Drying:

6 test specimens measuring 10×10 cm and made of flat woven cotton areprewashed in a Tergotometer for 20 minutes at 23° C. with the abovelaundering formula; the water used has a hardness of 30°HT (dilutedContrexéville® mineral water); the amount of laundry detergent employedis 5 g per liter of water; the number of test specimens per pot is 6.

The squares of fabric are subsequently rinsed 3 times for 5 minutes(each time), twice with cold water and the third time with cold water towhich either 7 ml of commercial rinsing formula FR or 7.3 ml of therinsing formulas FRI2 or FRII2 have been added.

The squares of fabric are subsequently wrung out and then dried onclotheshorses.

(b) Staining:

4 drops of dirty motor oil (DMO) are deposited on the test specimensprewashed as above.

To ensure good fixing of the stains, the soiled fabrics are placed in anoven at 60° C. for 1 hour.

To allow effective reproducibility of the results, the fabrics arewashed within 24 hours.

(c) Washing/Rinsing/Drying:

The soiled tests specimens are washed, rinsed, wrung and dried under thesame conditions as those described in (a).

Evaluation

The reflectance of the fabrics before and after washing is measuredusing a Dr. Lange/Luci 100 colorimeter. The efficacy of the test polymeras a soil release agent is evaluated by the percentage elimination ofthe stains, calculated by the formulaE in %=100×(R3−R2)/(R1−R2)where

-   R1 represents the reflectance before washing of the unsoiled fabric    (step (a))-   R2 represents the reflectance before washing of the soiled fabric    (steps (a) and (b))-   R3 represents the reflectance after washing of the soiled fabric    (steps (a), (b) and (c))

For each test product the mean percentage stain elimination iscalculated.

The results obtained are as follows: Rinsing formulation Cotton E in %FR 55 FRI2 61 FRII2 68

A significant enhancement of the removal of stains of the dirty motoroil type is observed when xanthan gum is employed as vehicle.

1. Formulation (F) intended for use in an operation of rinsing (R)textile fiber articles (S) by means of an aqueous or aqueous-alcoholicmedium (MR), said formulation (F) comprising at least one activesubstance (A) comprising at least one solid or liquid organic ororganosilicon material in particulate form and a vehicle (V) comprisingat least one organic polymer, capable of taking said active substance(A) to the surface of said textile fiber articles (S) in the rinsingoperation (R), in the form: of a stable dispersion, with a pH of from 2to 5, of said active substance (A) in an aqueous or aqueous-alcoholicmedium (MAV) comprising said vehicle (V), or in a solid form obtained bydrying said dispersion,  the nature of the active substance (A), of theaqueous or aqueous-alcoholic medium (MAV), and of the vehicle (V) beingsuch that the active substance (A) is insoluble in the medium (MAV), hasan overall zero or cationic charge in the medium (MAV), is stabilized inthe medium (MAV) by means of a cationic surfactant (TAC), it beingpossible for said cationic surfactant (TAC) to be wholly or partlyreplaced by a nonionic surfactant when the material constituting theactive substance (A) is intrinsically cationic or intrinsicallypotentially cationic in the medium (MAV), remains insoluble in therinsing medium (MR); the vehicle (V) is soluble or dispersible in themedium (MAV) and in the rinsing medium (MR) has an overall cationic orzero ionic charge in the medium (MAV), at the pH of the rinsingoperation in the rinsing medium (MR) is capable of developing anioniccharges in sufficient quantity to destabilize the active substance (A)in the rinsing medium (MR).
 2. Formulation according to claim 1),characterized in that the rinsing medium (MR) has a pH of from 5.5 to 8.3. Formulation according to claim 1) or 2), characterized in that thematerial constituting the active substance (A) is an oil or a meltablesolid.
 4. Formulation according to any one of claims 1) to 3),characterized in that the particles of active substance (A) have anaverage diameter ranging from 10 nm to 200 μm, preferably from 10 nm to5 μm and more preferably from 10 nm to 2 000 nm.
 5. Formulationaccording to any one of claims 1) to 4), characterized in that theactive substance (A) comprises material having lubricating propertieswith regard to textile fiber articles.
 6. Formulation according to anyone of claims 1) to 5), characterized in that the material constitutingthe active substance (A) is a polyorganosiloxane selected from nonionicpolyorganosiloxanes polyorganosiloxanes having at least one cationic orpotentially cationic function in the medium (MAV) amphotericpolyorganosiloxanes having at least one cationic or potentially cationicfunction in the medium (MAV) and at least one function which is neutralin the medium (MAV) and potentially anionic in the rinsing medium (MR)polyorganosiloxanes having at least one function which is neutral in themedium (MAV) and potentially anionic in the rinsing medium (MR). 7.Formulation according to any one of claims 1) to 6), characterized inthat the material constituting the active substance (A) is anα-ω-bis(hydroxy)polydimethylsiloxane, anα-ω-bis(trimethyl)polydimethylsiloxane, a polymethylphenylsiloxane or acyclic polydimethylsiloxane, preferably in oil form.
 8. Formulationaccording to any one of claims 1) to 6), characterized in that thematerial constituting the active substance (A) is an aminopolyorganosiloxane.
 9. Formulation according to claim 8), characterizedin that the amino polyorganosiloxane is a polyorganosiloxane which hashindered piperidyl groups.
 10. Formulation according to any one ofclaims 6) to 9), characterized in that said polyorganosiloxane islinear.
 11. Formulation according to any one of claims 1) to 5),characterized in that the active substance (A) comprises a materialselected from mono-, di- or triglycerides of C₁-C₃₀ carboxylic acids ormixtures thereof, such as vegetable oils sugar esters, sucroglycerides—C₁-C₃₀ alcohol esters of C₁-C₃₀ carboxylic or C₂-C₃₀ dicarboxylic acidsethylene or propylene glycol monoesters or diesters of C₁-C₃₀ carboxylicacids propylene glycol C₄-C₂₀ alkyl ethers di(C₈-C₃₀ alkyl) ethersorganic waxes comprising alkyl chains containing 4 to 40 carbon atoms.12. Formulation according to any one of claims 1) to 11), characterizedin that the ratio of the mass of polymer constituting the activesubstance (A) to the mass of surfactant (TAC) is from 0.01 to 10,preferably from 0.01 to
 1. 13. Formulation according to any one ofclaims 1) to 12), characterized in that the cationic charges generatedby the optional cationic or potentially cationic units of the materialconstituting the active substance (A) and by the cationic surfactant orsurfactants at the surface of the material constituting the activeactive substance (A) in dispersion in the medium (MAV) are such that thezeta potential of said polymer or copolymer in dispersion in (MAV) isfrom 0 to +50 mV, preferably from +10 to +40 mV.
 14. Formulationaccording to any one of claims 1) to 13), characterized in that thedispersion medium (MAV) for the active substance (A) is water or anaqueous-alcoholic polar medium.
 15. Formulation according to claim 14),characterized in that the alcohol or alcohols present in theaqueous-alcoholic polar medium represent up to 70% of the volume of themedium (MAV).
 16. Formulation according to any one of claims 1) to 15),characterized in that the polymer constituting the vehicle (V) is anypolymer which is soluble or dispersible in aqueous or aqueous-alcoholicmedium with a pH of between 2 and 8 and which comprises at least oneunit which is neutral in the medium (MAV) and potentially anionic (HA)in the rinsing medium (MR).
 17. Formulation according to claim 16),characterized in that the vehicle (V) polymer further comprises at leastone unit which is cationic or potentially cationic (HC) in the medium(MAV) and/or at least one hydrophilic or hydrophobic nonionic unit. 18.Formulation according to any one of claims 1) to 17), characterized inthat the relative amounts of the various units of the polymerconstituting the vehicle (V) are such that in the medium (MAV) theoverall charge of the polymer or copolymer is zero or cationic. 19.Formulation according to any one of claims 1) to 18), characterized inthat the relative amounts of vehicle (V) polymer, surfactant (TAC), andmaterial constituting the active substance (A) are such that in thecourse of the rinsing operation the number of anionic charges developedin the rinsing medium (MR) by the vehicle polymer (V) is sufficient todestabilize the active substance (A) in the rinsing medium (MR), inparticular by electrostatic attraction with the surface charges of theactive substance (A) in the medium (MR).
 20. Formulation according toclaim 19), characterized in that the number of anionic charges developedin the rinsing medium (MR) by the vehicle (V) polymer to destabilize theactive substance is at least 1% relative to the number of cationicsurface charges of the active substance (A) in the medium (MR), and notmore than 200% relative to the number of cationic surface charges of theactive substance (A) in the medium (MR).
 21. Formulation according toany one of claims 1) to 20), characterized in that the polymerconstituting the vehicle (V) is a polymer selected from polymers derivedfrom ethylenically unsaturated monomers, potentially anionic naturalpolysaccharides, potentially anionic or amphoteric substituted ormodified polysaccharides, or mixtures thereof.
 22. Formulation accordingto any one of claims 1) to 21), characterized in that the polymerconstituting the vehicle (V) is a polymer derived: from at least one α-βmonoethylenically unsaturated monomer which is neutral in the medium(MAV) and potentially anionic (HA) in the rinsing medium (MR) andoptionally at least one α-β monoethylenically unsaturated monomer whichis cationic or potentially cationic (HC) in the medium (MAV), andoptionally at least one nonionic α-β monoethylenically unsaturatedmonomer which is hydrophilic or hydrophobic, preferably hydrophilic. 23.Formulation according to any one of claims 1) to 22), characterized inthat the polymer constituting the vehicle (V) is a random, block orgraft copolymer derived: from at least one α-β monoethylenicallyunsaturated hydrophilic monomer which is neutral in the medium (MAV) andpotentially anionic (HA) in the rinsing medium (MR) and from at leastone α-β monoethylenically unsaturated hydrophilic monomer which iscationic or potentially cationic (HC) in the medium (MAV), andoptionally from at least one nonionic α-β monoethylenically unsaturatedmonomer which is hydrophilic or hydrophobic, preferably hydrophilic. 24.Formulation according to any one of claims 1) to 23), characterized inthat the polymer constituting the vehicle (V) derives from one or moreα-β monoethylenically unsaturated monomers and has an average molar massof greater than 5 000 g/mol, preferably from 20 000 to 500 000 g/mol.25. Formulation according to any one of claims 1) to 24), characterizedin that the polymer constituting the vehicle (V) is selected frompolyacrylic or polymethacrylic acids, alkali metal polyacrylates orpolymethacrylates, preferably with a molar mass by weight of from 100000 to 1 000 000 g/mol acrylic acid/DADMAC copolymers, with a molarratio of 50/50 to 30/70, preferably with a molar mass by weight of from70 000 to 350 000 g/mol acrylic acid/MAPTAC copolymers, with a molarratio of 60/40 to 30/70, preferably with a molar mass by weight of from90 000 to 300 000 g/mol acrylic acid/MAPTAC/linear C₄-C₁₈ alkylmethacrylate terpolymers comprising 0.005 to 10% by mass of alkylmethacrylate, with an acrylic acid/MAPTAC molar ratio ranging from 60/40to 30/70, and preferably having a molar mass by weight of from 50 000 to250 000 g/mol acrylic acid/dimethylaminoethyl methacrylate (DMAEMA)copolymers, with a molar ratio of 60/40 to 30/70, preferably with amolar mass by weight of from 50 000 to 300 000 g/mol.
 26. Formulationaccording to any one of claims 1) to 21), characterized in that thepolymer constituting the vehicle (V) is a potentially anionic naturalpolysaccharide formed of nonionic monosaccharide units and ofmonosaccharide units which are neutral in the medium (MAV) andpotentially anionic in the rinsing medium (MR), and are alike ordifferent.
 27. Formulation according to claim 26), characterized in thatsaid potentially anionic natural polysaccharide is a branchedpolysaccharide formed of a main chain comprising alike or differentanhydrohexose units and of branches comprising at least oneanhydropentose and/or anhydrohexose unit which is neutral in the medium(MAV) and optionally potentially anionic in the rinsing medium (MR). 28.Formulation according to claim 26) or 27), characterized in that saidpotentially anionic natural polysaccharide is a xanthan gum, asuccinoglycan, a rhamsan, a gellan gum or a welan gum.
 29. Formulationaccording to any one of claims 26) to 28), characterized in that saidpotentially anionic natural polysaccharide has a molar mass by weight offrom 2 000 to 5 000 000, preferably from 10 000 to 5 000 000, moreparticularly from 10 000 to 4 000 000 g/mol.
 30. Formulation accordingto any one of claims 1) to 21), characterized in that the polymerconstituting the vehicle (V) is a substituted or modified polysaccharidewhose native skeleton is formed of nonionic monosaccharide units and/orof monosaccharide units which are neutral in the medium (MAV) andpotentially anionic in the rinsing medium (MR), said monosaccharideunits being alike or different and being substituted or modified by oneor more groups which carry at least one charge which is neutral in themedium (MAV) and potentially anionic in the medium (MR) and optionallyby one or more groups which carry at least one charge which is cationicor potentially cationic in the medium (MAV),  the degree of substitutionor modification of the monosaccharide units by the entirety of thegroups which carry charges which are potentially anionic and of optionalgroups which carry cationic charges being such that said substituted ormodified polysaccharide is soluble or dispersible in aqueous oraqueous-alcoholic medium and has an overall cationic or zero charge inthe medium (MAV).
 31. Formulation according to claim 30), characterizedin that said substituted or modified polysaccharide further comprises atleast one nonionic modifying or substituent group.
 32. Formulationaccording to claim 30) or 31), characterized in that said substituted ormodified polysaccharide is a substituted or modified branchedpolysaccharide whose native skeleton is formed of a main chaincomprising alike or different anhydrohexose units and of branchescomprising at least one anhydropentose and/or anhydrohexose unit whichis neutral in the medium (MAV) and optionally potentially anionic in therinsing medium (MR),  the anhydrohexose and/or anhydropentose units ofsaid polysaccharide being substituted or modified by one or more groupswhich carry at least one charge which is neutral in the medium (MAV) andpotentially anionic in the medium (MR) and optionally at least onecharge which is cationic or potentially cationic in the medium (MAV),the degree of substitution or modification DSi of the anhydrohexoseand/or anhydropentose units by the entirety of said groups which carrycharges which are ionic or potentially ionic ranging from 0.01 to lessthan 3, preferably from 0.01 to 2.5, with a ratio of the number ofpotentially anionic charges in the medium (MR) to the number of cationicor potentially cationic charges in the medium (MAV) ranging from 100/0to 30/70, preferably from 100/0 to 50/50.
 33. Formulation according toany one of claims 29) to 32), characterized in that said substituted ormodified polysaccharide has a molar mass by weight of from 2 000 to 5000 000, preferably from 10 000 to 5 000 000 g/mol.
 34. Formulationaccording to any one of claims 29) to 33), characterized in that thenative skeleton of said substituted or modified polysaccharide is agalactomannan.
 35. Formulation according to any one of claims 29) to34), characterized in that the native skeleton of said substituted ormodified polysaccharide is selected from carboxymethylgalactomannans,especially carboxymethylguars, carboxymethylhydroxypropylgalactomannans,especially carboxymethylhydroxypropylguars,carboxymethyl-hydroxypropyltrimethylammonium chloride galactomannans,especially carboxymethylhydroxypropyltrimethylammonium chloride guars,carboxymethylhydroxypropyl-hydroxypropyltrimethylammonium chloridegalactomannans, especiallycarboxymethyl-hydroxypropylhydroxypropyltrimethylammonium chlorideguars.
 36. Formulation according to any one of claims 1) to 35),characterized in that the amount of vehicle (V) present in saidformulation is from 0.01 to 5 parts by weight, preferably from 0.001 to4 parts by weight, and more particularly from 0.05 to 2 parts by weightper 100 parts by weight of active substance (A).
 37. Formulationaccording to any one of claims 1) to 36), characterized in that it is inthe form of an aqueous or aqueous-alcoholic dispersion comprising per100 parts of its weight: from 0.01 to 40, preferably from 0.05 to 30parts by dry weight of active substance (A) from 0.01 to 50, preferablyfrom 0.01 to 35 parts by dry weight of surfactant (TAC) from 0.001 to 4,preferably from 0.01 to 1 part by dry weight of vehicle (V) polymer. 38.Formulation according to any one of claims 1) to 37), characterized inthat it further comprises one or more customary constituents of cationicrinsing formulations, selected from cationic softeners, opticalbrighteners, color transfer inhibitors, water-soluble monovalent mineralsalts, dyes, fragrances, foam suppressants, enzymes and bleaches. 39.Process for treating textile fiber articles by contacting said articlesin the course of a rinsing operation in aqueous or aqueous-alcoholicmedium with the rinsing formulation (F) of any one of claims 1) to 38),and recovering said rinsed articles.
 40. Process intended to enhance theantiwrinkle and/or easy-iron and/or soil release and/or abrasionresistance properties of textile fiber articles, which consists incontacting said articles in the course of a rinsing operation in aqueousor aqueous-alcoholic medium with the rinsing formulation (F) of any oneof claims 1) to 38), and in recovering said rinsed articles.
 41. Use ina formulation (F) intended for use in an operation of rinsing (R)textile fiber articles (S) by means of an aqueous or aqueous-alcoholicmedium (MR), formulation (F) comprising at least one active substance(A) comprising at least one liquid or solid organic or organosiliconmaterial in particulate form and being in the form of a stabledispersion with a pH of from 2 to 5 of said active substance (A) in anaqueous or aqueous-alcoholic medium (MAV) or in a solid form obtained bydrying said dispersion,  the nature of the active substance (A) and ofthe aqueous or aqueous-alcoholic medium (MAV) being such that the activesubstance (A) is insoluble in the medium (MAV) has an overall zero orcationic charge in the medium (MAV), is stabilized in the medium (MAV)by means of a cationic surfactant (TAC), it being possible for saidcationic surfactant (TAC) to be wholly or partly replaced by a nonionicsurfactant when the material constituting the active substance (A) isintrinsically cationic or intrinsically potentially cationic in themedium (MAV) remains insoluble in the rinsing medium (MR);  of at leastone organic polymer which is soluble or dispersible in the medium (MAV)and in the rinsing medium (MR) has an overall cationic or zero ioniccharge in the medium (MAV) and is capable, at the pH of the rinsingoperation in the rinsing medium (MR), of developing anionic charges insufficient quantity to destabilize the active substance (A) in therinsing medium (MR);  as a vehicle (V) capable of bringing said activesubstance (A) toward the surface of said textile fiber articles (S) inthe rinsing operation (R).
 42. Process for enhancing the deposition ofan active substance (A) comprising at least one solid or liquid organicor organosilicon material in particulate form on the surface of textilefiber articles (S), during an operation of rinsing of said articles bymeans of an aqueous or aqueous-alcoholic medium (MR) obtained from aformulation (F) comprising said active substance (A), the formulation(F) being in the form of a stable dispersion with a pH of from 2 to 5 ofsaid active substance (A) in an aqueous or aqueous-alcoholic medium(MAV) or in a solid form obtained by drying said dispersion,  the natureof the active substance (A) and of the aqueous or aqueous-alcoholicmedium (MAV) being such that the active substance (A) is insoluble inthe medium (MAV) has an overall zero or cationic charge in the medium(MAV), is stabilized in the medium (MAV) by means of a cationicsurfactant (TAC), it being possible for said cationic surfactant (TAC)to be wholly or partly replaced by a nonionic surfactant when thematerial constituting the active substance (A) is intrinsically cationicor intrinsically potentially cationic in the medium (MAV) remainsinsoluble in the rinsing medium (MR);  by adding to said formulation (F)a vehicle (V) comprising at least one organic polymer which is solubleor dispersible in the medium (MAV) and in the rinsing medium (MR) has anoverall cationic or zero ionic charge in the medium (MAV) and iscapable, at the pH of the rinsing operation in the rinsing medium (MR),of developing anionic charges in sufficient quantity to destabilize theactive substance (A) in the rinsing medium (MR).
 43. Processes accordingto any one of claims 40), 41) or 43), or use according to claim 42),characterized in that the amount of formulation employed, expressed interms of dry matter, is from 0.001 to 5 g/l, preferably from 0.05 to 2g/l in the rinsing bath.